1092944-14-3Relevant academic research and scientific papers
Oxidation of spirocyclohexyl-1,2,4-trithiolane and complexation reaction with [Pt(η2-nb)(PPh3)2]
Petzold, Holm,Braeutigam, Silvio,Goerls, Helmar,Weigand, Wolfgang,Romanski, Jaroslaw,Mloston, Grzegorz
, p. 5627 - 5632 (2008/09/17)
Oxidation of spirocylcohexyl-1,2,4-trithiolane 1 yielded the 4-S- and 1-S-oxide, 2 and 3, respectively. The complexation reactions of 1-3 with [Pt(η2-nb)(PPh3)2] (4; nb = norbornene) have been studied. The formed dithiolato, thioketone, thiolatosulfenato and sulfine complexes 5-8 have been isolated and characterized by 1H-, 31P NMR and IR spectroscopy and by mass spectrometry. The mechanism of the reaction is discussed. The reaction proceeds by insertion of the Pt 0 complex fragment into the sulfur-sulfur bond and subsequent ring contraction by extrusion of a thioketone or sulfine. Comparison of the molecular structures of the oxidized complexes 7 and 8 with the nonoxidized complex 5 shows elongation of the sulfenato-platinum bond and elongation of the platinum-phosphorus bond in the corresponding trans position. The product formed suggests that, in this system, formation of thiolato-platinum bonds is energetically favoured to sulfenato-platinum bonds. The structures of 5, 7 and 8 were established by X-ray crystallography. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
